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Environmental Pollution 152 (2008) 245e252

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Effect of microbial activity, soil water content and added copper

on the temporal distribution patterns of HCB and DDT among
different soil organic matter fractions
Jing-jing Zhang, Bei Wen, Xiao-quan Shan*
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences,
Chinese Academy of Sciences, PO Box 2871, Beijing 100085, China
Received 7 November 2006; received in revised form 24 April 2007; accepted 25 April 2007

Biological activity, soil moisture and Cu have different effects on HCB and DDT transfer from FA, HA and BHA
to lipid and IR fractions.

Abstract

Temporal changes in the distribution of exogenous HCB and DDT among different soil organic matter fractions were studied under sterile and
non-sterile conditions, different soil water contents, and different concentrations of added Cu2þ. The residence time was 311 days. Soil organic
matter was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions by a methyl
isobutyl ketone (MIBK) method. Results revealed that there is a mass transfer tendency of DDT and HCB from FA, HA and BHA to IR and lipid
fractions with increasing residence time. Microbial activity accelerated the mass transfer, while the addition of Cu2þ slowed it down. The HCB
and DDT transfer rate decreased as the soil moisture increased from 1.9% to 60%, but increased when soil moisture increased further to 90%.
A two-compartment first order kinetic model was used to describe the mass transfer from FA, HA and BHA.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Temporal distribution pattern; Soil organic matter fractions; Biological activity; Soil moisture; Copper; HCB; DDT

1. Introduction (Gustafsson et al., 1997; Cornelissen et al., 2005) and diffus-

Hexachlorobenzene (HCB) and dichlorodiphenyltrichloro-
ethane (DDT) are of great concern as typical hydrophobic or-
ganic pollutants (HOCs) due to their long half-life,
bioaccumulative nature and chronic adverse effects on humans
and animals. They have been detected in air, soil, fish, birds,
and even in human milk (Qiu et al., 2004). The sequestration
of DDT and HCB is of considerable interest because of its ef-
fect on bioavailability and the risk-assessment paradigms used
to guide management and cleanup of contaminated sites and
soil. The processes of HOCs sequestration in soil are thought
to be driven by partitioning into the soil organic matter (SOM)
* Corresponding author. Tel.: þ86 10 62923560; fax: þ86 10 62923563.
E-mail address: xiaoquan@rcees.ac.cn (X.-q. Shan).
ing into soil micropores (Farrell et al., 1999). In soil with
greater than 0.1% organic carbon content, partitioning into
SOM has been found to be the dominant process (Chiou
et al., 2000; Kang and Xing, 2005).
Among the SOM fractions, humin is considered to be the
most important one (Kohl and Rice, 1998; Macleod and Sem-
ple, 2003). Several investigations deemed that as residence
time increases, HOCs tend to transfer from FA and HA frac-
tions to humin (Weber and Huang, 1996; Bogan and Trbovic,
2003). Moreover, HOCs associated with humin exhibit more
resistance to desorption and less bioavailability (Chiou et al.,
2000; Nam and Kim, 2002; Kang and Xing, 2005). In our pre-
vious study (Zhang et al., 2007), a MIBK isolation technique
(Kohl and Rice, 1998) was applied to fractionate SOM into fu-
lic acid (FA), humic acid (HA) and humin fractions, and then

0269-7491/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2007.04.026
246 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252
humin was further isolated into bound humic acid (BHA),
lipid and insoluble residue (IR) fractions. The CPMAS 13C
NMR spectra of HA, BHA, lipid, and IR convincingly re-
vealed different carbon-type distributions among these humic
fractions. Moreover, as residence time increased, the contents
of DDT and HCB in the FA, HA and BHA fractions decreased,
while those in the IR and lipid fractions increased.
Besides soil organic type and content (Bogan and Trbovic,
2003; Kang and Xing, 2005), many environmentally relevant
factors affect mass transfer of HOCs in soil, such as hydropho-
bic porosity (Nam and Alexander, 1998), microbial activity
(Carmichael et al., 1997; Macleod and Semple, 2003), soil
moisture (Gupta and Gajbhiye, 2002), soil aggregation (Nam
et al., 2003) and co-existing metal ions (Yuan and Xing,
2001; Feng et al., 2006). The effect of microbial activity on
the mass transfer of HOCs was ascribed to partial transforma-
tion and/or carbon turnover activities of the soil microbial
communities (Guthrie and Pfaender, 1998; Macleod and Sem-
ple, 2003). Water is the medium that organic contaminants dif-
fuse to binding sites within soil aggregates, and may have
a particularly complicated effect on the mass transfer of or-
ganic compounds in soils (Gaillardon and Dur, 1995; Pigna-
tello, 1998). Soil water not only competes for adsorption on
soil minerals (Gaillardon and Dur, 1995), but also changes
the properties of SOM (Pignatello, 1998), hence influences
the affinity of SOM for HOCs, desorption hysteresis and se-
questration of HOCs (Xing and Pignatello, 1997). Heavy
metals and organic contaminants often coexist in soils. The
negatively charged surfaces of humic materials tend to bind
metal ions, which reduce the negative charge and contribute
to an improvement in the hydrophobic property of humic sub-
stances (Saison et al., 2004). Moreover, metal cations often en-
courage humic substances to adopt a coiled configuration and
possess glassy properties, leading to greater sorption capacity
and non-linearity, and higher desorption hysteresis (Yuan and
Xing, 2001; Wrobel et al., 2003; Feng et al., 2006).
Although extensive evidence indicated that microbial activ-
ity, water content and coexisting metals affected the sequestra-
tion of HOCs, there is little information on the effects of those
factors on the temporal distribution pattern of HOCs among
various SOM fractions. Therefore, the aim of this work was
to study the temporal distribution of HCB and DDT among
various SOM fractions as affected by those environmentally
relevant factors to better understand the sequestration process
of HCB and DDT in soils. The two-compartment first order ki-
netic model was used to describe the transfer of HCB and
DDT from each SOM fraction. The implications of such tem-
poral distribution change for the soil environment are
discussed.
2. Materials and methods
2.1. Soil samples
Soil used in this study was collected from Heilongjiang province of
China (Isohumisols, 5.48% organic carbon, pH 7.35). The soil was air-dried,
ground, and passed through a 2-mm sieve. The air-dried soil contained 1.9%
of water content, and background Cu content of soil was 10.2 mg kg1.
Cation-exchange capacity (CEC) determined by the BaCl2 method (Hender-
shot and Duquette, 1986) was 25.6 cmol kg1. All subsoil samples were sealed
in glass bottles and stored at room temperature for subsequent analysis and
experiments.
2.2. HCB and DDT spiking and aging
2.2.1. Experiment 1: study on the effect of microbial activity
One hundred grams of air-dried and sterilized (by 60Co irradiation,
2.5 Mrad) soil samples in triplicate were spiked with 200 mg of HCB and
DDT in 10 ml hexane, blended and placed in a hood to evaporate hexane
for 5 h. Non-sterilized soil samples treated with the same spiking were used
for comparison.
2.2.2. Experiment 2: study on the effect of soil water
The second 100 g of air-dried and sterilized soil samples in triplicate
spiked with 200 mg of HCB and DDT in 10 ml hexane as described above
were saturated with sterilized distilled water to bring the moisture level to
30%, 60% and 90% of its water holding capacity, respectively. During the
course of this study, sterilized distilled water was added to compensate for
the loss of water.
2.2.3. Experiment 3: study on the effect of added Cu2þ
Various amounts of Cu solution (Cu(NO3)2$3H2O, guaranteed reagent
grade) were added to the third 100 g of air-dried and sterilized soil samples
in triplicate to 200, 500 and 1000 mg g1 Cu, respectively. The concentrations
of Cu added represent the Cu-contaminated soil from low to high levels (Wang
et al., 2007; Niklińska et al., 2006). After mixed thoroughly, the soils were
spiked with 200 mg of HCB and DDT in 10 ml hexane and evaporated as de-
scribed above.
All the soil samples were sealed in solvent-rinsed microcosms (1-kg Kilner
jar) and sterilized, and then incubated at 20  C and stored in the dark for dif-
ferent time intervals. During the incubation time, the soils were sterilized ev-
ery 2 months to maintain the sterility.
2.3. Fractionation of SOM substances
SOM were operationally fractionated into FA, HA, BHA, lipid, and IR
fractions according to the MIBK technique described by Kohl and Rice
(1998). The whole procedure is summarized in Fig. 1.
Briefly, 10 g incubated soil sample was first mixed with 200 ml of 0.5 M
NaOH and shaken under nitrogen for 24 h. The sample was centrifuged for
30 min and the supernatant containing FA and HA was separated. The residue
precipitate was then briefly stirred with an additional 50 ml of 0.5 M NaOH
and centrifuged for 30 min. The supernatant containing FA and HA was
Soil
0.5 M NaOH Extraction
Soluble Insoluble
Aqueous
Add MIBK and H2O; pH of the aqueous
layer was adjusted to below 2 by HCl
Aqueous
Add NaOH
Add HCl to bring
the pH below 2
Add H2O
Soluble Insoluble Aqueous MIBK contains Precipitate
contains FA contains HA contains BHA lipid contains IR
Fig. 1. Sequence of steps in the MIBK method.
 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252
combined with FA and HA obtained from the previous procedure. This stir and
centrifugation operation was repeated five times. FA and HA were further sep-
arated by acidifying to a pH < 2 with concentrated HCl and centrifuging. The
aqueous phase was referred to as FA and the precipitate was HA.
The humin fraction with soil residue was transferred to a separatory funnel
along with 200 ml of de-ionized water and 200 ml of MIBK. The mixture was
acidified to about pH 2 by concentrated HCl, shaken vigorously for about
1 min, and allowed to equilibrate for about 1 h. The aqueous phase containing
FA and precipitate was separated from MIBK. Then FA and precipitate were
further separated from each other by centrifuging, and FA was combined
with the FA fraction obtained above. The residue precipitate was transferred
with 200 ml of 0.5 M NaOH to the same separatory funnel, shaken vigorously
and allowed to stand again for 1 h. BHA entered the alkaline aqueous phase,
and was then separated from the precipitate. The precipitate was returned to
the separatory funnel again with 200 ml of de-ionized water, shaken vigor-
ously for about 1 min, and allowed to equilibrate overnight. The aqueous phase
and precipitate were discharged, and further separated from each other by cen-
trifugation. BHA in the supernatant was combined with the BHA fraction ob-
tained above. The precipitate contained the IR fraction. The MIBK phase
contained the lipid fraction.
2.4. Analysis of organic carbon in each SOM fraction
The organic carbon contents of the FA and BHA fractions were analyzed
with a Phoenix 8000 total organic carbon analyzer (Tekmar-Dohrmann Co.,
Cincinnati, OH, USA) after residual MIBK had been removed by evaporation.
While those of the HA, lipid and IR fractions were determined by the
WalkleyeBlack titration (Nelson and Sommers, 1982) after evaporation of all
organic solvent or water.
2.5. Determination of HCB and DDT in SOM fractions
HCB and DDT in the soil, HA, BHA and IR fractions were extracted by
the Soxhlet extraction method. Frozen dried HA, BHA or IR fraction, or
2.00 g of soil sample was ground with 10.00 g of anhydrous Na2SO4 in a mor-
tar and pestle prior to Soxhlet extraction. The ground mixture was placed in
a thimble filter and extracted with 100 ml of 1:1 (v/v) hexane/acetone for
24 h at 5e6 min cycle1. HCB and DDT in FA were extracted three times
with 200 ml of hexane in a separatory funnel for 24 h (Nam and Kim, 2002).
The extracts and MIBK were concentrated to about 1e2 ml by a rotary
evaporator, and further purified with a chromatographic column (15 mm
length  10 mm i.d.) loaded with 10 g activated Florisil (60e100 mesh, Wenz-
hou Chemical Reagent Factory, China). The elution was subsequently carried
out using 100 ml hexane containing 10% acetone (v/v). After concentrating to
near dryness in a rotary evaporator, the elution was diluted with n-hexane, and
brought to exactly 1.0 ml under a gentle stream of pure nitrogen for gas chro-
matographic analysis.
The concentrations of HCB and DDT were analyzed with a GC (Agilent
6890N, Agilent Technologies, Inc., Wilmington, DE, USA) equipped with
a Nickel 63 electron capture detector (mECD) and a HP-5 fused silica capillary
column (30 m length  0.32 mm i.d.  0.25 mm film thickness, J&W Scien-
tific Co., Folsom, CA, USA). The oven temperature program started at
60  C (holding time 1 min), increased to 140  C at 15  C/min, and finally pro-
grammed to 280  C at 8  C/min (holding time 5 min). The temperature of the
injector and detector was 220 and 300  C, respectively. High purity nitrogen
was used as both carrier (2.0 ml min1) and makeup (60.0 ml min1) gas.
Samples (1 ml) were injected under splitless injection mode. The concentra-
tions of HCB and DDT were determined by comparing the peak area of the
samples with the calibration curves of the standards.
2.6. Quality control and quality assurance
Strict quality control was employed for the extraction and analysis. Deca-
chlorobiphenyl (DCBP) was added to the fractionated samples before HCB
and DDT extraction and purification as a surrogate. Recoveries of the surrogate
standards from the FA, HA, BHA, lipid and IR fractions were 89e96%, 92e
98%, 84e91%, 97e99%, and 91e95%, respectively.
247
Standards of HCB (C6Cl6, purity 99.9%) and DDT (2,2-bis-(4-chloro-
phenyl)-1,1,1-trichloroethane, purity 98%) were purchased from Aldrich Inc.
(USA), and used as received without further purification. All reagents used
were of pesticide grade. The concentrations of HCB and DDT were quantita-
tively determined by external standard method using peak area mode with
2,4,5,6-tetrachloro-m-xylene as internal standard added before GC-ECD deter-
mination. The detection limits (DL) of HCB and DDTs were determined at
signal-to-noise ratio (S/N ) of 3. The HCB and DDT recoveries were deter-
mined based on the peak area ratio of direct injection of extract to the working
standards prepared in hexane.
The concentrations of HCB and DDT in soils and each soil fraction were
determined immediately after spiking and solvent evaporated. The average
recoveries of HCB and DDT ranged from 92% to 101% and 90% to 98%, re-
spectively, indicating the accuracy and homogeneity of the spiking. The rela-
tive standard deviation (RSD) values of the contents of HCB and DDT in six
replicated fractionations were in the range of 2.4e16.3%. The instrument de-
tection limits of HCB and DDT were 0.04 and 0.1 mg l1, respectively. The
sum of the HCB and DDT in the five fractions was comparable with the total
HCB and DDT contents obtained by Soxhlet extraction of the soils, showing
good reproducibility of the fractionation and determination performance. The
data confirmed the practicability of the fractionation and analytical protocols
of HCB and DDT in various SOM fractions and in soils.
2.7. Transfer kinetics model
A two-compartment first-order kinetic model was used for the description
of mass transfer of HCB and DDT from the FA, HA and BHA fractions (Wa-
tanabe et al., 2005).
qðtÞ
¼ Fr expð kr tÞ þ ð1  Fr Þexpð ks tÞ ð1Þ
q0
where Fr is the percentage of HCB or DDT of the rapid transfer fraction con-
trolled by expanded SOM region, while (1  Fr) is the percentage of the slow
transfer fraction controlled by condensed region, kr and ks are the correspond-
ing apparent first order rate constants of rapid and slow transfer, respectively.
3. Results and discussion
3.1. Spiking of HCB and DDT to soils
Over the given residence time intervals of 1, 7, 14, 30, 90,
120, 184 and 311 days, the recoveries in the sterilized soil
were 92e99% and 88e96% for HCB and DDT, respectively,
suggesting that the loss and degradation of HCB and DDT,
as well as the formation of bound residues, during sequestra-
tion were negligible. For the non-sterilized soil, over the initial
30 days of residence, the recoveries of HCB and DDT were
90e98% and 89e94%, respectively. However, when the resi-
dence time exceeded 30 days, the recoveries of HCB and DDT
were decreased to 76e92% and 75e88%, respectively. The
possible reasons are discussed in the following section.
3.2. Effect of biological activity on the distribution
of HCB and DDT among SOM fractions
The distribution of HCB and DDT among various SOM
fractions of the sterilized and non-sterilized soils with resi-
dence period is shown in Fig. 2. For the sterilized soil, as
the residence time increased, HCB and DDT decreased in
the FA, HA and BHA and increased in the lipid and IR frac-
tions, suggesting a mass transfer of HCB and DDT from the
248 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252

(a) (b) than biodegradation was the main explanation. Other studies
FA
also revealed that microbial activity may promote the forma-
FA
tion of bound residue, thus decreasing the extractability and
2 2 bioavailability of HOCs in soil (Carmichael et al., 1997;
Guthrie and Pfaender, 1998; Macleod and Semple, 2003).
The mass transfer of DDT and HCB from FA, HA and BHA
0 0
fit the two-compartment first-order kinetic model very well
8 HA
6
HA with all the R2 higher than 0.97 (Table 1). A significant differ-
ence was found between rapid mass transfer rates (kr) values,
Distribution of HCB among SOM fractions

Distribution of DDT among SOM fractions

4 3 whereas slow mass transfer rate (ks) values of non-sterilized
soil were higher than that of sterilized soil. Both FA and HA
0 0 fractions are believed to consist of two distinct regions for
BHA 6 BHA
HOC sorption: the expanded (rubbery) region which is respon-
8
sible for rapid mass transfer and the condensed (glassy) region
3
which is responsible for slow mass transfer (Pignatello and
4
Xing, 1996; Schaumann and Leboeuf, 2005). The unchanged
kr and increased ks values suggest that the microbial activity
0 0
could enhance HCB and DDT mass transfer by encouraging
HCB and DDT to move into the condensed organic matrix.
40
64 It has been reported that compared with those in sterile soil,
HOCs in non-sterile soil showed greater levels of sequestration
lipid 32
lipid (more extensive decreases in extractability and bioavailability)
56
(Carmichael et al., 1997; Richnow et al., 1998). Macleod and
60 Semple (2003) found that there was a significant increase in
32 the rate and extent of sequestration of pyrene in the biologi-
55 cally active soils than that in sterile soil. Guthrie and Pfaender
24 (1998) also found that the extractability of pyrene in biologi-
IR IR
50 cally active soils decreased to a greater extent than in NaN3-
0 100 200 300 0 100 200 300
amended soil. Although there is growing observations of the
Residence time (day) Residence time (day) role of microorganisms on the sequestration or mass transfer
of HOCs in soil, the mechanisms are not fully understood.
Fig. 2. Distribution patterns of HCB (a) and DDT (b) in each SOM fraction The possible mechanisms may be ascribed to the partial trans-
under (,) sterilized and (B) non-sterilized regimes as a function of residence
time.
formation (Richnow et al., 1997) and/or the carbon turnover
activities by the soil microbial communities (Guthrie and
Pfaender, 1998; Richnow et al., 1998; Howsam et al., 2001).
FA, HA and BHA to the lipid and IR fractions. In the initial
30 days, there were no significant differences in the HCB
and DDT distribution between the sterilized and non-sterilized
soils. Nevertheless, significant decreases of HCB and DDT in
the lipid and IR fractions of the non-sterilized regime were ob- Table 1
Mass transfer rate parameters of HCB and DDT in the sterilized and non-
served with increasing residence time from 90 to 300 days.
sterilized soils
This is in accordance with the low recoveries of total DDT
Fr kr (days1) ks (days1) R2
and HCB concentrations.
Two possible reasons may be responsible for the low recov- Sterilized
HCB FA 0.724  0.031a* 0.644  0.051a 0.050  0.004a 0.971
eries of DDT and HCB: biodegradation and the formation of
HA 0.706  0.023a 0.284  0.031a 0.004  0.001a 0.987
‘‘bound residues’’. It is well documented that increased con- BHA 0.694  0.047a 0.097  0.016a 0.002  0.001a 0.978
tact time led to increased sequestration and reduced biodegra- DDT FA 0.811  0.033a 1.226  0.186a 0.058  0.010a 0.986
dation of HOCs (Bogan and Sullivan, 2003; Macleod and HA 0.781  0.020a 0.273  0.012a 0.015  0.002a 0.997
Semple, 2003). HOCs associated with humin fraction ex- BHA 0.672  0.027a 0.237  0.021a 0.007  0.002a 0.997
hibited more resistance to desorption and have less bioavail- Non-sterilized
ability (Pignatello and Xing, 1996; Nam and Kim, 2002). HCB FA 0.707  0.025a 0.705  0.114a 0.071  0.004b 0.976
Thus, if the biodegradation is the main reason, larger decreases HA 0.697  0.058a 0.257  0.045a 0.011  0.003b 0.988
BHA 0.703  0.102a 0.108  0.067a 0.005  0.001b 0.977
of HCB and DDT should be found in the FA and HA fractions. DDT FA 0.783  0.041a 1.512  0.123a 0.082  0.009b 0.984
However, this phenomenon was not observed in this study. In HA 0.802  0.053a 0.294  0.016a 0.021  0.003b 0.991
view of the low recoveries and the decrease of HCB and DDT BHA 0.658  0.047a 0.256  0.031a 0.013  0.002b 0.977
in the lipid and IR fractions with an increasing contact time, *Values in the columns for the same compound followed by the same letter are
we could deduce that the formation of bound residues rather not statistically different (p > 0.05).
 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252 249

3.3. Effect of soil humidity on the distribution of HCB Table 2

and DDT among SOM fractions Mass transfer rate parameters of HCB and DDT for soils at different moisture
levels

Fig. 3 delineates the distribution of HCB and DDT among Water Fr kr (days1) ks (days1) R2
content
SOM fractions as a function of residence time under different
soil moisture conditions. Their mass transfer rates calculated 1.9% HCB
FA 0.724  0.031a* 0.644  0.051a 0.050  0.004a 0.971
from Eq. (1) are listed in Table 2. As the soil water content in- HA 0.706  0.023a 0.284  0.031a 0.004  0.001a 0.987
creased from 1.9% to 30%, the mass transfer rates (kr and ks BHA 0.694  0.047a 0.097  0.016a 0.002  0.001a 0.978
values) of HCB and DDT from FA, HA, and BHA fractions DDT
decreased obviously. When the water content increased from FA 0.811  0.033a 1.226  0.086a 0.058  0.010a 0.986
30% to 60%, kr and ks values decreased further (with some ex- HA 0.781  0.020a 0.273  0.012a 0.015  0.002a 0.997
BHA 0.672  0.027a 0.237  0.021a 0.007  0.002a 0.997
ceptions). However, when the water content increased to 90%,
no decreases but some increases of kr and ks values were 30% HCB
FA 0.603  0.059b 0.231  0.054b 0.011  0.002b 0.981
found. The kr and ks values of FA, HA and BHA were the
HA 0.649  0.061a 0.100  0.022b 0.002  0.001a 0.964
same or even higher than those of 1.9% water content. In BHA 0.620  0.026a 0.043  0.003b 0.001  0.000a 0.996
the meantime, when the water content was 90%, the contents DDT
of HCB and DDT in the lipid fraction were the same as those FA 0.533  0.059b 0.175  0.045b 0.007  0.001b 0.982
of 60% water content, whereas HCB and DDT in the IR frac- HA 0.653  0.055a 0.089  0.017b 0.004  0.001b 0.976
BHA 0.636  0.053a 0.100  0.018b 0.003  0.001b 0.983
tion were higher than those of 1.9% water content.
Previous studies suggested that humin provided the ‘‘inter- 60% HCB
nal surface’’ of a soil particle and rendered partially inaccessi- FA 0.662  0.075b 0.099  0.021c 0.006  0.002c 0.956
HA 0.657  0.038a 0.048  0.006c 0.001  0.001a 0.973
ble to the bulk solution phase by overlayers of HA and FA BHA 0.467  0.052a 0.047  0.011b 0.001  0.000a 0.989
DDT
FA 0.594  0.054b 0.072  0.013c 0.002  0.001c 0.984
(a) (b) HA 0.651  0.032a 0.051  0.005c 0.001  0.001b 0.991
4 BHA 0.456  0.026b 0.056  0.007c 0.001  0.000c 0.990
FA 4 FA
90% HCB
2 2 FA 0.914  0.146a 0.785  0.041d 0.089  0.014a 0.971
HA 0.867  0.059d 0.367  0.014d 0.017  0.001d 0.987
BHA 0.669  0.078a 0.121  0.056a 0.011  0.001b 0.978
0 0 DDT
10 HA
FA 0.854  0.077a 1.345  0.037a 0.058  0.015a 0.983
HA 8
HA 0.812  0.109a 0.358  0.032d 0.032  0.003d 0.997
Distribution of HCB among SOM fractions

Distribution of DDT among SOM fractions

BHA 0.739  0.096a 0.346  0.087a 0.012  0.002a 0.992

5 4
*Values in the columns for the same compound followed by the same letter are
not statistically different ( p>0.05).
0 0

10 BHA 6 BHA (Weber and Huang, 1996; Bogan and Trbovic, 2003). Gradual
contaminant migration into micropores presented in this por-
5 3 tion, as well as the mineral portion itself, controlled the degree
and rate of sequestration (Xing and Pignatello, 1997). When
0 0 the soil moisture is raised, many of the micropores and meso-
42 pores of the fixed pore system are filled with water (Pignatello,
64 1998). Before organic compounds reach the sorption ‘‘sites’’
36 on these pores, they must travel through the water to reach
lipid lipid the surfaces of pores. This would lead to an aqueous hindrance
56
30 of organic compounds diffusing into soil pores or competition
of organic compounds with water for specific sorption sites.
33 60 As a result, when the soil moisture content increased, slower
mass transfer of HCB and DDT from the FA, HA and BHA
fractions were observed. On the contrary, when the soil mois-
22 IR 50 IR ture content was further increased to 90% of its water holding
capacity, the conformation of FA and HA may be modified and
0 100 200 300 0 100 200 300 became more swollen or expanded (Pignatello, 1998), result-
Residence time (day) Residence time (day) ing in a smaller degree of affinity, less non-linearity and hys-
Fig. 3. Distribution patterns of HCB (a) and DDT (b) in each SOM fraction at
teresis than the condensed humic materials (Xing and
(,) 1.9%, (B) 30%, (6) 60% and (7) 90% of soil water content levels as Pignatello, 1997; Feng et al., 2006). As BHA exhibited more
a function of residence time. similar characteristics to HA and may act as an outer layer
250 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252

of soil organic matter, the same effect of water on HCB and rigid molecules or molecular configurations (Maurice and
DDT transfer from BHA may be observed. Under this circum- Namjesnik-Dejanovic, 1999; Yuan and Xing, 2001; Feng
stance, HCB and DDT were more readily transferred from the et al., 2006), and rendering the reactive hydrophobic areas
FA, HA and BHA fractions compared with the air-dried soil. more accessible for HCB and DDT adsorption because of
the coagulation of the most polar areas (Xing and Pignatello,
3.4. Effect of copper on the distribution of HCB and DDT 1997; Wrobel et al., 2003; Saison et al., 2004). The configura-
among SOM fractions tion-changed FA and HA possess glassy properties, higher af-
finity, greater sorption capacity and non-linearity, and high
Fig. 4 shows the distribution patterns of HCB and DDT desorption hysteresis (Yuan and Xing, 2001; Wrobel et al.,
among SOM fractions in the presence of different concentra- 2003; Feng et al., 2006). The penetration of HCB and DDT
tions of coexisting Cu2þ. Their mass transfer rates calculated into these configuration-changed FA and HA contributed to
from Eq. (1) are listed in Table 3. As the concentration of the enhanced affinity of the FA and HA fractions for HCB
Cu2þ added increased, the mass transfer rates (kr and ks values) and DDT and decreased the HCB and DDT mass transfer
of HCB and DDT from FA, HA, and BHA fractions decreased. rate from these fractions with the increase of added Cu2þ. Al-
Correspondingly, the contents of HCB and DDT in the lipid though there are no reports dealing with the interaction be-
and IR fractions increased. tween BHA and Cu2þ so far, based on the similar
This may be attributed to the interactions between Cu2þ characteristics to HA, one can hypothesize that the added
and SOM. It is suggested that the metallic cations could Cu2þ might have the same effect on BHA.
change the structure of FA and HA through complexation
with functional polar groups of organic matter (such
as -COOH and -OH), leading to smaller, denser, and more 4. Conclusions

Although many studies have focused on the distribution of

(a) (b) organic compounds among the FA, HA and humin fractions,
3.0
3.0 direct observation of temporal distribution change of HCB
FA FA
and DDT in various SOM fractions especially in humin, under
1.5 1.5 various environmental conditions such as microbial activity,
soil moisture and coexisting metals is lacking. Based on the
0.0
above study one can draw the following conclusions:
0.0
10 8
HA HA (1) HCB and DDT mass transfer was primarily a physical pro-
Distribution of HCB among SOM fractions

Distribution of DDT among SOM fractions

cess over the initial residence period of <30 days, with the
5 4 activity of microbial communities becoming more obvious
after 1 month of incubation, which accelerated the mass
0 0 transfer;
8 BHA BHA (2) Medium level of soil moisture (30% and 60% of water
6
holding capacity) impeded HCB and DDT to transfer
4 3
from the FA, HA and BHA to the lipid and IR fractions,
whereas at high moisture level (90% of water holding ca-
0 0 pacity), the transfer rate was enhanced, implying that agri-
culture activity such as irrigation and natural events such
40 as flooding in summer may influence the fate of HCB
63
and DDT in the environment;
lipid lipid
(3) Coexisting Cu2þ slowed down the mass transfer of HCB
32
and DDT from SOM fractions, suggesting that at locations
54 where both heavy metal and organic compounds pollutions
occurred, the mass transfer rate of HCB and DDT would
30
56 be reduced with increasing contents of heavy metals.
Thus the impacts of heavy metals should be taken into
IR IR consideration when the transportation and fate of HOCs
in the environment are to be predicted.
20 49
0 100 200 300 0 100 200 300
Incubation time (day) Incubation time (day) Although the fractionation procedure may somewhat alter
the existing distribution of HCB and DDT in SOM fractions,
Fig. 4. Distribution patterns of HCB (a) and DDT (b) in each SOM fraction
of soils with various concentrations of Cu2þ as a function of incubation this study was expected to provide additional convincing
time: (,) 35.5 mg kg1, (B) 200 mg kg1, (6) 500 mg kg1, and (7) data on the contribution of different environmentally relevant
1000 mg kg1. conditions to the mass transfer of HCB and DDT in SOM, and
 J.-j. Zhang et al. / Environmental Pollution 152 (2008) 245e252 251

Table 3
Mass transfer rate parameters of HCB and DDT for soils with various concentrations of Cu fit by two-compartment first order kinetic model
Cu2þ added (mg kg1) Fr kr (days1) ks (days1) R2
0 HCB
FA 0.724  0.031a* 0.644  0.051a 0.050  0.004a 0.971
HA 0.706  0.023a 0.284  0.031a 0.004  0.001a 0.987
BHA 0.694  0.047a 0.097  0.016a 0.002  0.001a 0.978
DDT
FA 0.811  0.033a 1.226  0.086a 0.058  0.010a 0.986
HA 0.781  0.020a 0.273  0.012a 0.015  0.002a 0.997
BHA 0.672  0.027a 0.237  0.021a 0.007  0.002a 0.997
200 HCB
FA 0.699  0.055a 0.585  0.062a 0.032  0.008b 0.967
HA 0.536  0.053b 0.272  0.081a 0.005  0.001a 0.942
BHA 0.668  0.061a 0.089  0.023a 0.001  0.001a 0.931
DDT
FA 0.809  0.093a 0.913  0.015b 0.004  0.004b 0.958
HA 0.840  0.032a 0.169  0.017b 0.008  0.002b 0.992
BHA 0.707  0.072a 0.157  0.038b 0.004  0.001a 0.976
500 HCB
FA 0.608  0.022b 0.413  0.042b 0.018  0.006b 0.965
HA 0.684  0.084b 0.067  0.016b 0.001  0.001b 0.957
BHA 0.590  0.041a 0.056  0.008b 0.001  0.001a 0.984
DDT
FA 0.557  0.064b 0.608  0.107c 0.019  0.006b 0.951
HA 0.694  0.064b 0.128  0.026b 0.005  0.002b 0.982
BHA 0.757  0.057a 0.082  0.013c 0.002  0.001a 0.982
1000 HCB
FA 0.795  0.144b 0.101  0.029c 0.009  0.001b 0.912
HA 0.719  0.039b 0.045  0.004b 0.001  0.000b 0.993
BHA 0.553  0.033a 0.052  0.006b 0.001  0.000a 0.992
DDT
FA 0.713  0.085b 0.548  0.222c 0.018  0.008b 0.967
HA 0.674  0.077b 0.112  0.029b 0.005  0.002b 0.972
BHA 0.722  0.058a 0.084  0.014c 0.002  0.001a 0.978
*Values in the columns for the same compound followed by the same letter are not statistically different ( p > 0.05).

to present a new angle to assess the multi-domain sorption
concept.
Acknowledgments
This study was supported by the National Natural Science
Foundation of China (Grants 20377048 and 20237010).
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